CN101766981A - Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester - Google Patents
Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester Download PDFInfo
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- CN101766981A CN101766981A CN201010045636A CN201010045636A CN101766981A CN 101766981 A CN101766981 A CN 101766981A CN 201010045636 A CN201010045636 A CN 201010045636A CN 201010045636 A CN201010045636 A CN 201010045636A CN 101766981 A CN101766981 A CN 101766981A
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Abstract
The invention discloses a method for preparing a polymer microsphere by utilizing rosin and crylic acid hydroxy ester, which comprises the following steps of: mixing an ethenyl monoacid monomer with ester matter prepared by the preparation method of the invention the application number of which is 200710085381.8 in the weight ratio of 1 to 20:1 to produce a monomer mixture; adding deionized water and a dispersion stabilizer the mass of which is 0.1 to 20 percent, relative to the mass of the monomer mixture, to a reactor provided with a condenser, a thermometer and a stirrer and then heating to 90 DEG C to completely dissolve, wherein the mass ratio of the monomer mixture to the deionized water is 100:10 to 80; adding the monomer mixture and an initiator the mass of which is 0.1 to 20 percent, relative to the mass of the monomer mixture after cooling to about 80 DEG C; after heating for 3 hours at constant temperature, heating to 90 DEG C and then reacting for 2 hours; washing products with distilled water after cooling, and drying in a baking oven after filtering to obtain the light yellow polymer microsphere. In the invention, the natural resources of China are sufficiently utilized to increase the additional value of rosin; the polymer microsphere is prepared by adopting a non-toxic environment-friendly method; and the obtained products can be used in various occasions of adsorption and separation.
Description
Technical field
The present invention relates to a kind of method of utilizing rosin and crylic acid hydroxy ester to prepare polymer microballoon, particularly a kind of method of utilizing rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate to prepare polymer microballoon.
Technical background
Polymer microballoon be meant diameter at nanoscale to micron order, the macromolecular material that is shaped as sphere or other solid or polymer composite.Polymer microballoon is widely used in fields such as plastics, coating, biomedicine, electronic information.The preparation method of polymer microballoon is varied, is that the preparation method of the polymer microballoon of raw material has emulsion polymerisation, suspension polymerisation, dispersin polymerization and precipitation polymerization etc. with the monomer.Its used monomer mainly contains: vinyl, phenylethylene, (methyl) esters of acrylic acid, (methyl) acrylamide monomers, and epoxies monomer and vinyl acetate esters monomer etc.If when polymerization, add the monomer of the difunctional of copolymerization with it, then can obtain crosslinked polymer microballoon, improve the intensity and the stability of polymer microballoon greatly.
Rosin is made up of various kinds of resin acid and little fat acid and neutral substance, and wherein main component is a resin acid, accounts for more than 90% of its total amount.Resin acid has the luxuriant and rich with fragrance shelf structure of three-membered ring, two two keys and a carboxyl, has characteristics such as easy oxidation, acid number are higher, poor heat stability, directly uses and is subjected to certain restriction.Utilize reaction active groups such as carboxyl in the rosin molecular structure, conjugated double bond can give rosin various performances by reactions such as esterification, addition, polymerizations.The thick grade of thunderous good fortune people is raw material synthesizing maleated rosin EDIA-acrylic copolymer with maleic rosin EDIA and acrylic acid; People such as Lin Mingtao utilize rosin and acrylic acid addition reaction to prepare acrylic acid rosin, again it is carried out chloride and esterification has prepared acrylic acid rosin (acrylic acid-2-hydroxyethyl ester) ester, prepared the copolymer of this ester and methyl methacrylate (MMA) by the mini-emulsion polymerization mode; People such as Zuo Zhenyu utilize rosin and maleic acid reaction synthesizing maleated rosin, the esterification synthesizing maleated rosin propylene alcohol ester under the catalyst condition with maleic rosin and propenyl makes maleic rosin propenyl ester polymer with maleic rosin propylene alcohol ester by the alchlor initiated polymerization again; People such as Xiaoli Zhang carry out esterification with rosin acid and propenyl, and separation of polymeric obtains polymerized rosin propenyl ester polymer and oxide thereof again.Human Forals such as Yu Caili and methacrylic acid-beta-hydroxy ethyl ester carry out esterification and have obtained carboxylate, then to its carried out in toluene the radically homo reaction and with methyl methacrylate (MMA) or with the copolyreaction of styrene (St), prepared homopolymers and copolymer.And the method for utilizing rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate to prepare polymer microballoon is not appeared in the newspapers at present.
Summary of the invention
The purpose of this invention is to provide a kind of is the method that cross-linking monomer prepares polymer microballoon with rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate.
Utilization of the present invention contains the rosin and crylic acid addition product of two carboxyls, carry out esterification with methacrylic acid-beta-hydroxy ethyl ester, obtain containing the macromonomer of two suspended double bond, this macromonomer can carry out copolyreaction with styrene or methacrylate monomers, owing to contain two two keys, can be used as the crosslinking agent of styrene or methacrylic acid polyisocyanate polyaddition in copolyreaction, its effect is equal to divinylbenzene.
Concrete steps are as follows:
1. be that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate with rosin, acrylic acid, methacrylic acid-beta-hydroxy ethyl ester, abbreviate carboxylate as, (application number is that 200710085381.8 patent of invention name is called " utilizing rosin and crylic acid hydroxy ester to prepare the method for carboxylate ").
2. the carboxylate that vinyl monobasic monomer and step (1) are made is that 1～20: 1 ratio is mixed and made into monomer mixture with mass ratio; In the reactor that condenser, thermometer, agitator are housed, add with the monomer mixture mass ratio be 100: 10～80 deionized water and with respect to the dispersion stabilizer of monomer mixture quality 0.1-20%, be heated to 90 ℃ of dissolvings fully; Cool to after about 80 ℃ and to add monomer mixture and with respect to the initator of monomer mixture quality 0.1-2%; After the heated at constant temperature 3 hours, be warming up to 90 ℃ and react end in 2 hours again; After the cooling product is washed with distilled water, filter back drying in baking oven, obtain light yellow polymer microsphere;
Described vinyl monobasic monomer is a kind of in styrene and the methacrylate;
Described dispersion stabilizer is a kind of in polyvinyl alcohol, gelatin and the polyvinylpyrrolidone;
Described initator is a kind of in azodiisobutyronitrile and the benzoyl peroxide.
Polymer microballoon outward appearance by the present invention's preparation is faint yellow, and particle diameter is at 100-1000um.
With rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate is that the binary cross-linking monomer prepares polymer microballoon, compare with the divinylbenzene that uses in the conventional polymer microballoon preparation process, have following characteristics: make full use of the natural resources of China, increase the added value of rosin; Adopt nontoxic and eco-friendly method preparation; Products therefrom can be used for adsorbing and the various occasions of separating.
The specific embodiment
Embodiment 1:
1. be that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate with rosin, acrylic acid, methacrylic acid-beta-hydroxy ethyl ester, abbreviate carboxylate as.
2. the carboxylate that styrene and step (1) are made is that 1: 1 ratio is mixed and made into monomer mixture with mass ratio; Add 60ml deionized water and 0.25 gram polyvinyl alcohol in the reactor that condenser, thermometer, agitator are housed, water-bath is heated to 90 ℃ of dissolvings fully.Cool to about 80 ℃ again, add the azodiisobutyronitrile of 20 gram monomer mixtures and 0.25 gram, the control mixing speed is 400r/min, and heated at constant temperature was warming up to 90 ℃ and reacts end after 2 hours again after 3 hours.The cooling back is poured product in the beaker and with distilled water into and washed, and is dry in baking oven after filtering, and obtains faint yellow globular solids polymer.
Embodiment 2:
1. be that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate with rosin, acrylic acid, methacrylic acid-beta-hydroxy ethyl ester, abbreviate carboxylate as.
2. the carboxylate that styrene and step (1) are made is that 10: 1 ratio is mixed and made into monomer mixture with mass ratio; Add 70ml deionized water and 2.5 gram polyvinyl alcohol in the reactor that condenser, thermometer, agitator are housed, water-bath is heated to 90 ℃ of dissolvings fully.Cool to about 80 ℃ again, add the benzoyl peroxide of 25 gram monomer mixtures and 0.25 gram, the control mixing speed is 400r/min, and heated at constant temperature was warming up to 90 ℃ and reacts end after 2 hours again after 3 hours.The cooling back is poured product in the beaker and with distilled water into and washed, and is dry in baking oven after filtering, and obtains faint yellow globular solids polymer.
Embodiment 3:
1. be that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate with rosin, acrylic acid, methacrylic acid-beta-hydroxy ethyl ester, abbreviate carboxylate as.
2. the carboxylate that methyl methacrylate and step (1) are made is that 10: 1 ratio is mixed and made into monomer mixture with mass ratio; Add 80ml deionized water and 5 gram polyvinylpyrrolidones in the reactor that condenser, thermometer, agitator are housed, water-bath is heated to 90 ℃ of dissolvings fully.Cool to about 80 ℃ again, add the azodiisobutyronitrile of 30 gram monomer mixtures and 0.5 gram, the control mixing speed is 400r/min, and heated at constant temperature was warming up to 90 ℃ and reacts end in 2 hours again after 3 hours.The cooling back is poured into product in the beaker and with the distilled water washing, is placed on drying in the baking oven after the filtration, obtains faint yellow globular solids polymer.
Embodiment 4:
1. be that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid addition product and crylic acid hydroxy ester carboxylate with rosin, acrylic acid, methacrylic acid-beta-hydroxy ethyl ester, abbreviate carboxylate as.
2. the carboxylate that styrene and step (1) are made is that 20: 1 ratio is mixed and made into monomer mixture with mass ratio; Add 60ml deionized water and 2.5 gram gelatin in the reactor that condenser, thermometer, agitator are housed, water-bath is heated to 90 ℃ of dissolvings fully.Cool to about 80 ℃ again, add 25 gram monomer mixtures and 0.5 gram benzoyl peroxide, the control mixing speed is 400r/min, and heated at constant temperature was warming up to 90 ℃ and reacts end in 2 hours again after 3 hours.The cooling back is poured into product in the beaker and with the distilled water washing, is placed on drying in the baking oven after the filtration, obtains faint yellow globular solids polymer.
Claims (1)
1. method of utilizing rosin and crylic acid hydroxy ester to prepare polymer microballoon, raw material comprises that with application number be rosin and crylic acid addition product and the crylic acid hydroxy ester carboxylate that the preparation method of 200710085381.8 patent of invention makes, abbreviate carboxylate as, it is characterized in that concrete steps are as follows:
The carboxylate that vinyl monobasic monomer and the preparation method who with application number is 200710085381.8 patent of invention are made is that 1～20: 1 ratio is mixed and made into monomer mixture with mass ratio; In the reactor that condenser, thermometer, agitator are housed, add with the monomer mixture mass ratio be 100: 10～80 deionized water and with respect to the dispersion stabilizer of monomer mixture quality 0.1-20%, be heated to 90 ℃ of dissolvings fully; Cool to after about 80 ℃ and to add monomer mixture and with respect to the initator of monomer mixture quality 0.1-2%; After the heated at constant temperature 3 hours, be warming up to 90 ℃ and react end in 2 hours again; After the cooling product is washed with distilled water, filter back drying in baking oven, obtain light yellow polymer microsphere;
Described vinyl monobasic monomer is a kind of in styrene and the methacrylate;
Described dispersion stabilizer is a kind of in polyvinyl alcohol, gelatin and the polyvinylpyrrolidone;
Described initator is a kind of in azodiisobutyronitrile and the benzoyl peroxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010045636A CN101766981A (en) | 2010-01-13 | 2010-01-13 | Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester |
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| CN201010045636A CN101766981A (en) | 2010-01-13 | 2010-01-13 | Method for preparing polymer microsphere by utilizing rosin and crylic acid hydroxy ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675517A (en) * | 2012-05-23 | 2012-09-19 | 桂林理工大学 | Preparation method of rosinyl magnetic polymer microspheres |
| CN102757714A (en) * | 2012-07-24 | 2012-10-31 | 江苏科技大学 | Ultraviolet curing coating for wood |
| CN103044616A (en) * | 2013-01-19 | 2013-04-17 | 桂林理工大学 | Preparation method of rosinyl carboxyl polymer microsphere |
| CN106995681A (en) * | 2017-04-05 | 2017-08-01 | 东莞市佳乾新材料科技有限公司 | A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof |
| CN109280137A (en) * | 2018-08-14 | 2019-01-29 | 桂林理工大学 | A kind of preparation method of abietyl TDI type aqueous polyurethane microballoon |
| CN111116848A (en) * | 2019-12-31 | 2020-05-08 | 河南省科学院高新技术研究中心 | Malathion ester modified acrylate emulsion, multifunctional easy-alkaline-washing adhesive and preparation method |
-
2010
- 2010-01-13 CN CN201010045636A patent/CN101766981A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675517A (en) * | 2012-05-23 | 2012-09-19 | 桂林理工大学 | Preparation method of rosinyl magnetic polymer microspheres |
| CN102757714A (en) * | 2012-07-24 | 2012-10-31 | 江苏科技大学 | Ultraviolet curing coating for wood |
| CN102757714B (en) * | 2012-07-24 | 2014-07-02 | 江苏科技大学 | Ultraviolet curing coating for wood |
| CN103044616A (en) * | 2013-01-19 | 2013-04-17 | 桂林理工大学 | Preparation method of rosinyl carboxyl polymer microsphere |
| CN103044616B (en) * | 2013-01-19 | 2015-06-17 | 桂林理工大学 | Preparation method of rosinyl carboxyl polymer microsphere |
| CN106995681A (en) * | 2017-04-05 | 2017-08-01 | 东莞市佳乾新材料科技有限公司 | A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof |
| CN106995681B (en) * | 2017-04-05 | 2018-09-18 | 东莞市佳乾新材料科技有限公司 | A kind of modified gelatin acrylic resin adhesive of the microballoon containing rosin polymer and preparation method thereof |
| CN109280137A (en) * | 2018-08-14 | 2019-01-29 | 桂林理工大学 | A kind of preparation method of abietyl TDI type aqueous polyurethane microballoon |
| CN109280137B (en) * | 2018-08-14 | 2021-01-12 | 桂林理工大学 | Preparation method of rosin-based TDI (toluene diisocynate) type waterborne polyurethane microsphere |
| CN111116848A (en) * | 2019-12-31 | 2020-05-08 | 河南省科学院高新技术研究中心 | Malathion ester modified acrylate emulsion, multifunctional easy-alkaline-washing adhesive and preparation method |
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Application publication date: 20100707 |